CN107001724B - The peroxide of liquid and the protection of the incipient scorch of fusible solid grade - Google Patents

The peroxide of liquid and the protection of the incipient scorch of fusible solid grade Download PDF

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CN107001724B
CN107001724B CN201580066454.1A CN201580066454A CN107001724B CN 107001724 B CN107001724 B CN 107001724B CN 201580066454 A CN201580066454 A CN 201580066454A CN 107001724 B CN107001724 B CN 107001724B
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organic peroxide
preparation
peroxide
liquid
mono
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CN107001724A (en
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L·H·帕莱斯
W·P·帕弗莱克
P·R·德鲁兹尼斯奇
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Arkema Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F118/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F118/02—Esters of monocarboxylic acids
    • C08F118/04—Vinyl esters
    • C08F118/08—Vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/242—Applying crosslinking or accelerating agent onto compounding ingredients such as fillers, reinforcements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • C08K5/08—Quinones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2331/00—Characterised by the use of copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
    • C08J2331/02—Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
    • C08J2331/04—Homopolymers or copolymers of vinyl acetate

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The embodiment of organic peroxide preparation provides longer time of scorch and protects and require less additive.These peroxide preparations may include, such as, at least one organic peroxide, at least one compound (for example, 4- hydroxyl-TEMPO) and at least one compound (for example, mono- tert-butyl hydroquinone) containing quinone containing NO free radical.The embodiment of the present invention is related to the organic peroxide composition comprising antiscorching agent.The embodiment of the present invention further relates to crosslinkable elastic composition, the method for solidifying these elastomers, and the product manufactured by this class method.

Description

The peroxide of liquid and the protection of the incipient scorch of fusible solid grade
Technical field
The present invention relates to for producing the liquid or fusible solid peroxide preparation with the protection of increased incipient scorch Composition and method, and the product manufactured by these methods.
Background technique
With the elastomer phase ratio of uncrosslinked thermoplastic and/or sulfur curable, when requiring final products to meet high machine When tool and desired physical considerations, such as improved heat ageing and lower remaining (permanent) pressure distortion, usually using organic peroxy Compound is for cross-linked thermoplastic polymer and elastomer and their mixture.Due to both thermoplastic and elastomer All be solid material at room temperature, in order to by free-radical crosslinking agent and any other desired by ingredient such as dyestuff, pigment, filling Agent, antioxidant, UV and heat stabilizer and the like are added in polymer, these polymer must and free-radical crosslinking agent With any other desired by ingredient it is sufficiently high with allow that polymer flows in mixing apparatus at a temperature of mechanically mix.
Crosslinking period and the time (time of scorch) being crosslinked from the free based precursor of addition until initial stage are depending on being used as friendship Join the rhermal decomposition rate (being conveniently expressed as half-life period) of the radical initiator of agent.Incipient scorch can be supplied to manufacture before starting Quotient is longer without the processing time for sacrificing final crosslinking rate or density, its benefit will be more because with the mixing of routine or Compounding method, such as grinding, Banbury (Banbury) squeeze out, when time and temperature relation lead to radical initiator can Incipient scorch starts when the decomposition of sight starts.If it is too early that this occurs, it is possible to create to the gel particle in the polymer blocks of mixture by This leads to the inhomogeneities of final product.Excessive coking reduces the plastic properties of material, so that it may no longer be processed, because This, leads to the loss of entire batch.
Several trials are had existed to extend time of scorch.U.S. the patent No. 5,245,084 discloses use and is suitable for The organic peroxide of cross linked thermoplastics and elastomer, these organic peroxides and quinhydrones and crosslinking accelerator it is specific Group combines, which is selected from crosslinking accelerator usually used in such applications.U.S. the patent No. 6,197,231 It teaches and combines quinhydrones, crosslinking to promote using radical initiator (azo initiator of organic peroxide or particular category) Agent and the combination of known sulphur release sulphur promotor are for extending time of scorch without to thermoplastic, elastomer and its mixed Close the curing time of object or the adverse effect of cured density.
There are (extended) organic peroxide preparations of the filler increment of several class of trade.However, due to The solubility of difference of the solid additive in organic peroxide, it is impossible to generate that enough incipient scorch protections are provided and are free of and fill out Fill the liquid peroxide preparation or uniformly fusible solid of agent or the filler containing relatively low amount.Will it is desirable that Organic peroxide preparation with the additive for possessing longer time of scorch and lower load capacity.
Summary of the invention
The embodiment of the present invention is related to the organic peroxide composition comprising antiscorching agent.The embodiment of the present invention further relates to Crosslinkable elastic composition, the method for solidifying these elastomers and the product manufactured by this class method.
Antiscorching agent 4- hydroxyl-TEMPO (4-OHT；4- hydroxyl -2,2,6,6- tetramethyl piperidine -1- oxygroup) and mono- tert-butyl Quinhydrones (MTBHQ) has the very limited solubility in organic peroxide.However, applicants unexpectedly send out The blend of both existing retarding agents (4-OHT and MTBHQ) provides longer time of scorch and less in organic peroxy The total additive needed in object preparation.This unexpected synergistic effect, when being total to for the compound using both classifications When mixed object, allow to be easier to be dissolved into peroxide by additive packet, since it is desired that significant less.
According to an embodiment of the invention, can produce uniform liquid and fusible solid peroxide preparation without Filler uses considerably less filler.It is filled out furthermore, it is possible to melt peroxide preparation or be sprayed to liquid formulations It fills in agent, if such form is desired.
The non-limiting example of the application of peroxide preparation of the invention includes using liquid and filler increment etc. HDPE roational molding of the organic peroxide of grade for crosslinking；The production of PEX- pipe；Injection-molded, compression molded, transmitting molding Crosslinking article；Electric wire and cable；Elastomer, rubber and the polymer being usually crosslinked；Modified polymer molecule amount and grafting Reagent such as maleic anhydride (MAH) and glycidyl methacrylate；For producing TPV, (thermoplasticity solidifies rubber to dynamical cure Glue)；And the rubber or foam of polymers of crosslinking.
The embodiment of the present invention is related to a kind of organic peroxide preparation, the preparation include following item, substantially by Following item composition is made of following item: at least one organic peroxide, at least one compound containing NO free radical (for example, 4-OHT) and at least one compound (for example, MTBHQ) containing quinone.Compared with the preparation of the prior art, this is matched Product provides longer time of scorch protection and less total additive.
The embodiment of the present invention further relates to a kind of elastic composition, which includes following item, substantially Be made of following item or be made of following item: at least one elastomer, at least one organic peroxide, at least one are nitrogenous The compound (for example, 4-OHT) of oxygen radical and at least one compound (for example, MTBHQ) containing quinone.
The embodiment of the present invention further relates to a kind of method for cured elastomer composition, and the method includes following Item is substantially made of following item or is made of following item: curing elastomer mixture in the presence of oxygen, wherein the elasticity Body composition includes following item, is substantially made of following item or is made of following item: at least one elastomer, at least one Organic peroxide, at least one compound (for example, 4-OHT) and at least one chemical combination containing quinone containing NO free radical Object (for example, MTBHQ).The embodiment of the present invention further relates to the product manufactured by this method.
Specific embodiment
Applicants have discovered that at least one compound (for example, 4-OHT) and at least one containing NO free radical The blend of compound (for example, MTBHQ) containing quinone provides the organic peroxide preparation with longer time of scorch, In less total additive is needed in the preparation.This unexpected synergistic effect, when the change using both classifications When closing the blend of object, allow to be easier to be dissolved into peroxide by additive packet, since it is desired that significant less.
One aspect of the present invention is related to a kind of organic peroxide preparation, which includes following item, substantially It is made of following item or is made of following item: at least one organic peroxide, at least one compound containing NO free radical (for example, 4- hydroxyl-TEMPO (4-OHT)) and at least one compound containing quinone are (for example, mono- tert-butyl hydroquinone (MTBHQ)).Compared with the preparation of the prior art, which provides longer time of scorch protection and less total Additive.
Thermal decomposition is subjected to known to all can generate that can cause the desired free radical for solidifying (crosslinking) reaction A little organic peroxides are all thought of as suitable for using preparation of the invention.Non-limiting example includes dialkyl group peroxide Compound, diperoxy base ketal, single peroxy carbonic ester, cyclic ketone peroxide, diacyl peroxide, organic sulfonyl peroxidating The peroxydicarbonate of the ambient-temp-stable of object, peroxyester and solid.In at least one embodiment, the organic peroxide It is selected from dialkyl peroxide, peroxy ketal, cyclic ketone peroxide, single peroxycarbonates, peroxyester and two acyls Base peroxide.
The peroxide title and physical characteristic of the organic peroxide of all these classes can be in Jose Sanchez With " organic peroxide (the Organic Peroxides) " of Terry N.Myers, Ke Ke-Ao Simo Chemical Engineering Technology encyclopaedia is complete Book (Kirk-Othmer Encyclopedia of Chemical Technology), fourth edition, volume 18 (1996) (it is draped over one's shoulders Dew content be incorporated herein by reference) in find.
Exemplary of dialkyl peroxide initiator includes:
Di-t-butyl peroxide；
Tert-butyl cumyl peroxide；
2,5- bis- (cumyl peroxy) -2,5- dimethylhexane；
2,5- bis- (cumyl peroxy) -2,5- dimethylhexyne -3；
4- methyl -4- (t-butylperoxy) -2- amylalcohol；
4- methyl -4- (t-amyl peroxy) -2- amylalcohol；
4- methyl -4- (cumyl peroxy) -2- amylalcohol；
4- methyl -4- (t-butylperoxy) -2 pentanone；
4- methyl -4- (t-amyl peroxy) -2 pentanone；
4- methyl -4- (cumyl peroxy) -2 pentanone；
2,5- dimethyl -2,5- two (t-butylperoxy) hexane；
2,5- dimethyl -2,5- two (t-amyl peroxy) hexane；
2,5- dimethyl -2,5- two (t-butylperoxy) hexin -3；
2,5- dimethyl -2,5- two (t-amyl peroxy) hexin -3；
2,5- dimethyl -2- t-butylperoxy -5- hydroperoxy hexane；
2,5- dimethyl -2- cumyl peroxy -5- hydroperoxy hexane；
2,5- dimethyl -2- t-amyl peroxy -5- hydroperoxy hexane；
Between/p- α, α-two [(t-butylperoxy) isopropyl] benzene；
1,3,5- tri- (tert butylperoxyisopropyl) benzene；
1,3,5- tri- (t-amyl peroxy isopropyl) benzene；
1,3,5- tri- (cumyl peroxy isopropyl) benzene；
Two [1,3- dimethyl -3- (t-butylperoxy) butyl] carbonic esters；
Two [1,3- dimethyl -3- (t-amyl peroxy) butyl] carbonic esters；
Two [1,3- dimethyl -3- (cumyl peroxy) butyl] carbonic esters；
Two-t-amyl peroxy compounds；
Dicumyl peroxide；
M- isopropenyl-the cumyl peroxide of t-butylperoxy-；
Tertiary pentyl cumyl peroxide；
Tert-butyl-isopropenyl cumyl peroxide；
2,4,6- tri- (butyl peroxy)-s- triazine；
1,3,5- tri- [1- (t-butylperoxy) -1- Methylethyl] benzene
1,3,5- tri--[(t-butylperoxy)-isopropyl] benzene；
1,3- dimethyl -3- (t-butylperoxy) butanol；
1,3- dimethyl -3- (t-amyl peroxy) butanol；And their mixture.
Other radical initiators that can be considered individually or with other present disclosures be used in combination two Alkyl peroxide is those of the group represented by being selected from by following below formula:
Wherein, R4And R5Between being independently in or contraposition is upper and be identical or different and selected from hydrogen or have 1 To the alkyl of the linear chain or branched chain of 6 carbon atoms.Dicumyl peroxide and isopropylcumyl cumyl peroxide are exemplary 's.
Other dialkyl peroxides include:
3- cumyl peroxy -1,3- dimethyl butyrate methyl acrylate；
3- t-butylperoxy -1,3- dimethyl butyrate methyl acrylate；
3- t-amyl peroxy -1,3- dimethyl butyrate methyl acrylate；
Three (1,3- dimethyl -3- t-butylperoxy butoxy) vinyl silanes；
1,3- dimethyl -3- (t-butylperoxy) butyl N- [1- { 3- (1- methyl ethylene)-phenyl } 1- methyl second Base] carbamate；
1,3- dimethyl -3- (t-amyl peroxy) butyl N- [1- { 3- (1- methyl ethylene)-phenyl } -1- methyl second Base] carbamate；
1,3- dimethyl -3- (cumyl peroxy) butyl N- [1- { 3- (1- methyl ethylene)-phenyl } -1- Methylethyl] Carbamate.
In the group of diperoxy base ketal initiator, preferred initiator includes:
1,1- bis- (t-butylperoxy) -3,3,5- trimethyl-cyclohexane；
1,1- bis- (t-butylperoxy) hexamethylene；
Normal-butyl 4,4- bis- (t-amyl peroxy) valerate；
Ethyl 3,3- bis- (t-butylperoxy) butyrate；
2,2- bis- (t-amyl peroxy) propane；
Four oxonane of 3,6,6,9,9- pentamethyl -3- ethoxy carbonyl methyl -1,2,4,5-；
Normal-butyl -4,4- bis(t-butylperoxy) valerate；
Ethyl -3,3- two (t-amyl peroxy) butyrate；And their mixture.
Illustrative solid, stable at room temperature peroxydicarbonate includes, but are not limited to: two (2- Phenoxyethyls) Peroxy dicarbonate；Two (4- tert-Butyl-cyclohexyl) peroxydicarbonates；Myristyl peroxy dicarbonate；Dibenzyl Base peroxydicarbonate；And two (isobornyl) peroxydicarbonate.It can be made according at least one embodiment of present disclosure Other peroxide include benzoyl peroxide, OO- tert-butyl-O- hydrogen-mono- peroxy-succinate and uncle OO- penta Base-O- hydrogen-mono- peroxy-succinate.
Illustrative cyclic ketone peroxide is the compound with following general formula (I), (II) and/or (III).
Wherein, R1To R10Independently selected from the following group, the group consisting of: hydrogen, C1 are to C20 alkyl, C3 to C20 ring To C20 alkaryl, these groups may include linear chain or branched chain alkane by alkyl, C6 to C20 aryl, C7 to C20 aralkyl and C7 Base characteristic and R1To R10It respectively can be replaced one or more groups selected from the following terms: hydroxyl, C1 to C20 alcoxyl Base, C1 to the C20 alkyl of linear chain or branched chain, C6 are such as used to C20 aryloxy group, halogen, ester, carboxyl, nitride and acylamino- In the peroxide mixture of cross-linking reaction total active oxygen content at least 20% will from formula (I), (II) and/or (III) compound.
Some examples of suitable cyclic ketone peroxide include:
Three peroxy nonane of 3,6,9, triethyl group -3,6,9- trimethyl -1,4,7- (or methyl-ethyl-ketone peroxide is cyclic annular Trimer), methyl-ethyl-ketone peroxide cyclic dimer and 3,3,6,6,9,9- vegolysen, tetra- oxa- ring of 2,4,5- Nonane.
The illustrative examples of peroxide base ester include:
2,5- dimethyl -2,5- two (benzoylperoxy) hexane；
TBPB tertiary butyl perbenzoate；
T-butyl peroxy yl acetate；
T-butylperoxy -2 ethyl hexanoic acid ester；
T-amyl perbenzoate；
T-amyl peroxy yl acetate；
T-butylperoxy isobutyrate；
3- hydroxyl -1,1- dimethyl tertiary butyl peroxy -2 ethyl hexanoic acid ester；
OO- tertiary pentyl-O- hydrogen-mono- peroxy succinate；
OO- tert-butyl-O- hydrogen-mono- peroxy succinate；
Di-t-butyl diperoxy base phthalic acid ester；
T-butylperoxy (3,3,5- tri-methyl hexanoic acid ester)；
Bis- (t-butylperoxycarbonyl) hexamethylenes of 1,4-；
T-butylperoxy -3,5,5 Trimethylhexanoic acid ester；
Tert-butyl-peroxy base-(cis- 3- carboxyl) propionic ester；
Allyl 3- methyl -3- t-butylperoxy butyrate.
It is exemplary list peroxy carbonic ester include:
OO- tert-butyl-O- isopropyl list peroxy carbonic ester；
OO- tert-butyl-O- (2- ethylhexyl) list peroxy carbonic ester；
1,1,1- tri- [2- (t-butylperoxy-carbonyl oxygroup) ethoxyl methyl] propane；
1,1,1- tri- [2- (t-amyl peroxy-carbonyl oxygroup) ethoxyl methyl] propane；
1,1,1- tri- [2- (cumyl peroxy-carbonyl oxygroup) ethoxyl methyl] propane；
OO- tertiary pentyl-O- isopropyl list peroxy carbonic ester.
Exemplary diacyl peroxide includes:
Two (4- methyl benzoyl) peroxide；
Two (3- methyl benzoyl) peroxide；
Two (2- methyl benzoyl) peroxide；
Didecanoyl peroxide；Dilauroyl peroxide；
The bromo- benzoyl peroxide of 2,4- bis-；
Succinic acid peroxide.
Dibenzoyl peroxide；
Two (2,4- dichloro-benzoyl) peroxide.
The imide peroxide of the type described in 9703961 A1 of PCT Application Publication WO (on 2 6th, 1997) Compound is it is also contemplated that be adapted for use with and being incorporated herein by reference.
Preferred peroxide includes one of following item or a variety of: 2,5- bis- (t-butylperoxy) -2,5- diformazan Base hexane；Tert-butyl cumyl peroxide；2,5- dimethyl -2,5- two (t-butylperoxy) hexin -3；T-butylperoxy- Isopropenyl cumyl peroxide；3,3,5,7,7- pentamethyl -1,2,4- trioxepan；3,6,9- triethyl group -3,6,9- Three peroxide nonane of trimethyl -1,4,7-；Between/p- two (t-butylperoxy) diisopropyl benzene；M- two (t-butylperoxies) Diisopropyl benzene；P- two (t-butylperoxy) diisopropyl benzene；Di-t-butyl peroxide；Two-t-amyl peroxy compounds； Dicumyl peroxide；1,1- bis- (t-butylperoxy) -3,3,5- trimethyl-cyclohexane；1,1- bis- (t-butylperoxy) ring Hexane；Normal-butyl 4,4- bis- (t-butylperoxy) valerate；Ethyl 3,3- bis- (t-butylperoxy) butyrate；The tertiary fourth of OO- Base-O- (2- ethylhexyl) list peroxy carbonic ester；OO- tert-butyl-O- isopropyl list peroxy carbonic ester；The poly- tert-butyl of polyethers Peroxy carbonic ester；Tert butyl peroxy benzoate；Tert-butyl hydroperoxide acetic acid esters；Tert-butyl hydroperoxide maleic acid；Two (4- Methyl benzoyl) peroxide；Dibenzoyl peroxide；Two (2,4 dichloro benzene formoxyl) peroxide；Peroxidating February Osmanthus acyl；Cumene hydroperoxide；And two (4- tert-butylcyclohexyl) peroxydicarbonate.
Preferred peroxide includes one of following item or a variety of: 2,5- bis- (t-butylperoxy) -2,5- two Methyl hexane；Tert-butyl cumyl peroxide；2,5- dimethyl -2,5- two (t-butylperoxy) hexin -3；T-butyl peroxy Base-isopropenyl cumyl peroxide；3,3,5,7,7- pentamethyl -1,2,4- trioxepan；Triethyl group -3,6 3,6,9-, Three peroxide nonane of 9- trimethyl -1,4,7-；Between/p- two (t-butylperoxy) diisopropyl benzene；M- two (t-butyl peroxy Base) diisopropyl benzene；P- two (t-butylperoxy) diisopropyl benzene；Di-t-butyl peroxide；Dicumyl peroxide； 1,1- bis- (t-butylperoxy) -3,3,5- trimethyl-cyclohexane；1,1- bis- (t-butylperoxy) hexamethylene；Normal-butyl 4,4- Two (t-butylperoxy) valerates；Ethyl 3,3- bis- (t-butylperoxy) butyrate；OO- tert-butyl-O- (2- ethyl hexyl Base) list peroxy carbonic ester；OO- tert-butyl-O- isopropyl list peroxy carbonic ester；The poly- t-butylperoxy carbonic ester of polyethers； Tert butyl peroxy benzoate；Dibenzoyl peroxide；Two (2,4 dichloro benzene formoxyl) peroxide；Cumene hydroperoxidation Object；And two (4- tert-butylcyclohexyl) peroxydicarbonate.
Even more preferably peroxide includes one of following item or a variety of: 2,5- bis- (t-butylperoxy) -2, 5- dimethylhexane；Tert-butyl cumyl peroxide；2,5- dimethyl -2,5- two (t-butylperoxy) hexin -3；Tert-butyl Peroxy-isopropenyl cumyl peroxide；3,3,5,7,7- pentamethyl -1,2,4- trioxepan；Between/p- two (tertiary fourth Base peroxy) diisopropyl benzene；M- two (t-butylperoxy) diisopropyl benzene；P- two (t-butylperoxy) diisopropyl Benzene；Di-t-butyl peroxide；Dicumyl peroxide；1,1- bis- (t-butylperoxy) -3,3,5- trimethyl-cyclohexane； 1,1- bis- (t-butylperoxy) hexamethylene；Normal-butyl 4,4- bis- (t-butylperoxy) valerate；Bis- (tert-butyl of ethyl 3,3- Peroxy) butyrate；OO- tert-butyl-O- (2- ethylhexyl) list peroxy carbonic ester；OO- tert-butyl-O- isopropyl list peroxide Base carbonic ester；Cumene hydroperoxide；Tert butyl peroxy benzoate；Dibenzoyl peroxide；And two (2,4 dichloro benzene Formoxyl) peroxide.
Most preferred peroxide includes one of following item or a variety of: 2,5- bis- (t-butylperoxy) -2,5- two Methyl hexane；Tert-butyl cumyl peroxide；2,5- dimethyl -2,5- two (t-butylperoxy) hexin -3；T-butyl peroxy Base-isopropenyl cumyl peroxide；Between/p- two (t-butylperoxy) diisopropyl benzene；M- two (t-butylperoxies) Diisopropyl benzene；P- two (t-butylperoxy) diisopropyl benzene；Dicumyl peroxide；Cumene hydroperoxide；1,1- bis- (t-butylperoxy) -3,3,5- trimethyl-cyclohexane；1,1- bis- (t-butylperoxy) hexamethylene；Bis- (uncle of normal-butyl 4,4- Butyl peroxy) valerate；Ethyl 3,3- bis- (t-butylperoxy) butyrate；OO- tert-butyl-O- (2- ethylhexyl) list mistake Oxygroup carbonic ester；OO- tert-butyl-O- isopropyl list peroxy carbonic ester；And tert butyl peroxy benzoate.
The example of the NO free radical (or " containing compound oxygen radical of nitrogen ") may include TEMPO (2,2,6,6- tetramethyl Piperidines -1- oxygroup) derivative, such as 4- hydroxyl TEMPO (4-OHT) and 4- acetamido TEMPO.As used herein, term " quinone " or " compound containing quinone " includes both quinone and quinhydrones and their ether, as the monoalky lether of quinhydrones, single aryl ether, Single aralkyl ethers and bis- (hydroxyalkyl) ethers.Can the non-limiting example of the quinone used in preparation of the invention include Mono- tertiary fourth quinhydrones (MTBHQ), quinhydrones, hydroquinone monomethyl ether (HQMME) (also referred to as 4- metoxyphenol), mono- amyl hydroquinone, Bis- (2- ethoxy) ethers of quinhydrones, 4- thanatol, 4- phenoxy phenyl, 4- (benzyloxy) phenol, bis- (the morpholino first of 2,5- Base) quinhydrones and benzoquinones.
Preferably the compound containing NO free radical includes 4- hydroxyl TEMPO (4-OHT) and TEMPO (2,2,6,6- tetra- Methyl piperidine 1- oxygroup).Preferably the compound containing quinone includes mono- tert-butyl hydroquinone (MTBHQ)；Quinhydrones；The mono- methyl ether of quinhydrones (HQMME), also referred to as 4- metoxyphenol (MEHQ)；Mono- amyl hydroquinone and two-amyl hydroquinones.
According to specific embodiment, organic peroxide preparation of the invention can further include at least one crosslinking and live Property auxiliary agent and/or at least one filler.According to specific embodiment, the example of cross linking co-agents includes methacrylic acid allyl Ester, triallyl cyanurate, triallyl isocyanurate, trimethylol-propane trimethacrylateThree hydroxyls Propane triDizinc acrylate resin and zinc dimethacrylate.
The additional non-limiting example of cross linking co-agents includes:
The coagent of the methyl acrylic ester type of Sartomer (Sartomer) manufacture, such as:
SR205H triethylene glycol dimethacrylate (TiEGDMA),
SR206H ethylene glycol dimethacrylate (EGDMA),
SR209 tetraethylene glycol dimethylacrylate (TTEGDMA),
SR210HH polyethylene glycol (200) dimethylacrylate (PEG200DMA),
SR214 1,4-butanediol dimethylacrylate (BDDMA),
SR231 dimethacrylate (DEGDMA),
SR239A 1,6-Hexanediol dimethacrylate (HDDMA),
SR252 polyethylene glycol (600) dimethylacrylate (PEG600DMA),
SR262 1,12- dodecanediol dimethacrylate (DDDDMA),
SR297J 1,3-BDO dimethylacrylate (BGDMA),
3 bisphenol a dimethacrylate (BPA3EODMA) of SR348C ethoxylation,
2 bisphenol a dimethacrylate (BPA2EODMA) of SR348L ethoxylation,
SR350D trimethylol-propane trimethacrylate (TMPTMA),
10 bisphenol a dimethacrylate (BPA10EODMA) of SR480 ethoxylation,
4 bisphenol a dimethacrylate (BPA4EODMA) of SR540 ethoxylation,
The alkoxylated pentaerythritol tetramethylacrylate of SR596 (PETTMA),
SR604 polypropylene glycol monomethacrylate (PPGMA),
SR834 Tricyclodecane Dimethanol dimethylacrylate (TCDDMDMA), and
The acid bifunctional auxiliary adhesion agent of SR9054；
The coagent of the acrylate type of Sartomer (Sartomer) manufacture, such as:
SR238 1,6- hexanediyl ester (HDDA),
SR259 polyethylene glycol (200) diacrylate (PEG200DA),
SR268G tetraethylene glycol diacrylate (TTEGDA),
SR272 triethylene glycol diacrylate (TIEGDA),
SR295 pentaerythritol tetraacrylate (PETTA),
SR306 tripropylene glycol diacrylate (TPGDA),
SR307 polybutadiene diacrylate (PBDDA),
SR341 3- methyl 1,5-PD diacrylate (MPDA),
SR344 polyethylene glycol (400) diacrylate (PEG400DA),
The high functional monomer of SR345 high-performance,
3 bisphenol a diacrylates (BPA3EODA) of SR349 ethoxylation,
SR351 trimethylolpropane trimethacrylate (TMPTA),
Bis--trimethylolpropane tetra-acrylate of SR355 (two TMPTTA),
SR368 tri- (2- ethoxy) isocyanurate triacrylate (THEICTA),
SR399 Dipentaerythritol Pentaacrylate (two PEPA),
(20) trimethylolpropane trimethacrylate (TMP20EOTA) of SR415 ethoxylation,
SR444 modified pentaerythritol triacrylate,
SR444D pentaerythritol triacrylate (PETIA),
3 trimethylolpropane trimethacrylates (TMP3EOTA) of SR454 ethoxylation,
Propenoxylated 3 trimethylolpropane trimethacrylate (TMP3POTA) of SR492,
4 pentaerythritol tetraacrylates (PETTA) of SR494 ethoxylation,
6 trimethylolpropane trimethacrylates (TMP6EOTA) of SR499 ethoxylation,
9 trimethylolpropane trimethacrylates (TMP9EOTA) of SR502 ethoxylation,
SR508 dipropylene glycol diacrylate (DPGDA),
SR534D polyfunctional acrylic ester (dedicated for sulfur curable),
1,10 decanediol diacrylate (DDDA) of SR595,
4 bisphenol a diacrylates (BPA4EODA) of SR601E ethoxylation,
10 bisphenol a diacrylates (BPA10EODA) of SR602 ethoxylation,
SR606A esterdiol diacrylate (EDDA),
SR610 Macrogol 600 diacrylate (PEG600DA),
The alkoxylated diacrylate of SR802,
SR833S Tricyclodecane Dimethanol diacrylate (TCDDMDA),
Propenoxylated 2 neopentylglycol diacrylate (PONPGDA) of SR9003,
Propenoxylated 3 glycerol tri-acrylate (GPTA) of SR9020,
15 trimethylolpropane trimethacrylates (TMP15EOTA) of SR9035 ethoxylation, and
12 glycerol tri-acrylates (G12EOTA) of SR9046 ethoxylation；
The special incipient scorch protection type of Sartomer (Sartomer) manufacture property auxiliary agent living, such as:
The methacrylate of 297F liquid incipient scorch protection,
The methacrylate of 350S liquid incipient scorch protection,
The methacrylate of 350W liquid incipient scorch protection,
The methacrylate of 500 liquid incipient scorch protection,
The methacrylate of 517 liquid incipient scorch protection, and
The methacrylate of 521 liquid incipient scorch protection；
The liquid high vinyl polybutadiene of Cray Valleylad Inc. (Cray Valley)；
Liquid polybutadiene；
PolyWithThe hydroxy-end capped liquid polybutadiene of series；
Ricon resin；For example,154；156MA17；
Functionalized liquid polybutadiene coagent, such as:
The functionalized polybutadiene of diallyl,
The functionalized polybutadiene of dimethylacrylate,
The functionalized polybutadiene of diacrylate
The coagent of allyl type, such as:
Triallylcyanurate (TAC),
Triallyl isocyanurate (TAIC),
Triallyl phosphate (TAP),
Triallyl borate (TAB),
Trimethyl allyl isocyanuric acid ester (TMAIC),
Diallyl terephthalate (DATP), also known as diallyl phthalate
Diallylcarbonate,
Diallyl maleate ester,
Diallyl fumarate,
Diallyl phosphite ester,
Trimethylolpropane allyl ether,
Poly- (diallyl isophthalic acid ester), and
Glyoxal bis- (diallyl acetals) (1,1,2,2- tetraallyloxyethane)；
The coagent of mixed type, such as:
Allkyl methacrylate,
Allyl acrylate,
Allkyl methacrylate oligomer,
Allyl acrylate oligomer, and
Sartomer SR523: new difunctional reactive's auxiliary agent (derivative of allkyl methacrylate or acrylate Object)；
2,4- diphenyl -4-methyl-1-pentene, also referred to as Nofmer MSD (α-methylstyrene dimer) are (from promise visitor Company (Nofco) is obtainable, it is especially useful in electric wire and cable application)；And
Other various cross linking co-agents, such as:
N, N '-metaphenylene dimaleimide, also referred to as HVA-2 (obtainable from E.I.Du Pont Company (DuPont)),
N, N '-to phenylene dimaleimide,
Cis- -1,2- polybutadiene (1,2-BR),
Divinylbenzene (DVB), and
4,4 '-(bismaleimide) diphenyl disulfides.
Preferred coagent includes the one or more of following item: 2,4- diphenyl -4-methyl-1-pentene, also referred to asMSD；Divinylbenzene；Triallylcyanurate；Triallyl isocyanurate；Trimethyl allyl isocyanide Urea acid esters；Triallyl phosphate；The 9102 tetraallyl oligourethane of CN 9101 and CN of Sartomer； Diallyl maleate ester；Diallyl fumarate；Tetraallyl pentaerythrite；Pentaerythritol triallyl ether；Three hydroxyl first Base propane trimethyl acrylic ester；Trimethylolpropane trimethacrylate；Allkyl methacrylate oligomer；1,4- fourth two Alcohol dimethylacrylate；N, N '-metaphenylene dimaleimide；The SR-523 trimethylolpropane diene of Sartomer Propyl methacrylate；Dizinc acrylate resin；Zinc dimethacrylate；297F；350S；350W；500；515；516HP；517HP；519HP；521HP；522；Liquid high vinyl polybutadiene；Liquid polybutadiene；PolyWithSerial is hydroxy-end capped Liquid polybutadiene；Resin；For example,154；And156MA17。
Non-limiting reality for optional inert filler used in the organic peroxide preparation of the invention Example includes the silicon of washing clay (for example, Burgers (Burgess) clay), the silica of precipitating, the calcium carbonate of precipitating, synthesis Sour calcium and their combination.The various combination of these fillers can be used to realize free flow in those skilled in the art Dynamic, non-caking final peroxide preparation.
According to specific embodiment, organic peroxide preparation of the invention may include silica-filled dose.
Organic peroxide preparation of the invention optionally including at least one additive selected from the group below, the group by The following terms composition: process oil (such as aliphatic process oil), processing aid, pigment, dyestuff, tackifier, wax, enhancing Auxiliary agent, UV stabilizer, foaming agent, activator, antiozonant and coagent are (for example, that sold by Sartomer A bit).
According to specific embodiment, the organic peroxide preparation include following item, be substantially made of following item or by Following item composition:
One or more organic peroxides between about 92wt% and about 98wt%,
One or more NO free radicals between about 1wt% and about 7wt%, and
Between about 1wt% and about 7wt% one or more quinones (one or more of them NO free radical and it is a kind of or The combined total amount of a variety of quinones is between about 2wt% and about 8wt%).
Of the invention one another embodiment provides a kind of elastic composition, which includes following Item is substantially made of following item or is made of the following terms:
At least one elastomer,
At least one organic peroxide,
At least one compound (for example, 4- hydroxyl-TEMPO (4-OHT)) containing NO free radical, and
At least one compound (for example, mono- tert-butyl hydroquinone (MTBHQ)) containing quinone.
In at least one embodiment, elastic composition of the invention may include a kind of elastomer of saturation, insatiable hunger The elastomer of sum, or saturation and both unsaturated elastomers blend.
According to specific embodiment, elastic composition of the invention further includes at least one polymer.The elastomer At least one polymer of composition may include a kind of polymer of saturation, unsaturated polymer, or saturation and insatiable hunger Both polymer of sum.
It should be noted that the elastomer of commercially available premixing can be used according to the present invention.These elastomers can wrap Containing multiple additives such as carbon black fillers, process oil, release agent, antioxidant and/or heat stabilizer.According to specific embodiment, At least one elastomer is a part comprising one of these additives or a variety of elastomer masterbatch.For example, elastic Body masterbatch may include following item, substantially be made of following item or be made of following item: at least one elastomer and it is a kind of or Multiple additives, these additives are selected from the group, which is made of following item: carbon black, polyethylene glycol, at least one process oil (for example, hold-up hydrocarbon, such as352), at least one antioxidant is (for example, 2,2,4- trimethyl -1,2- dihydro quinolines Quinoline, also referred to as TMQ), at least one release agent, at least one heat stabilizer and their combination.
As used in this, term " polymer " " refers to non-elastomer polymer, and the non-elastomer polymer is by extremely A kind of few monomer in polymerized form is constituted.Term " polymer " " includes homopolymer and copolymer, wherein term " copolymer " Refer to polymer, which is made of at least two different monomers in polymerized form.For example, according to present disclosure Copolymer can be the polymer including two kinds of different monomers, trimer or including three kinds of different monomers or more Polymer.
In at least one embodiment, the polymer of the elastic composition includes copolymer.These disclosed herein Embodiment lists the elastic composition including copolymer.However, such as those of ordinary skill in the art it can be readily appreciated that Homopolymer can be substituted in any embodiment including copolymer, unless clearly indicating on the contrary.
In at least one embodiment, which includes at least one elastomer and at least one copolymer. The elastomer and copolymer can with from 99:1 to 1:99, such as from 85:15 to 15:85 or from 75:25 to 25:75 model Weight ratio in enclosing is present in the elastic composition.In at least one embodiment, the elastomer and copolymer are with 50: 50 weight ratio is present in the elastic composition.In another embodiment, which includes the one of 100% Kind or a variety of elastomers and no one or more copolymers.
According at least one embodiment, which includes the elastomer of at least one saturation.The bullet of the saturation Property body can be selected from, for example, the not silicon rubber (Q) of degree of unsaturation, the poly- silicon oxygen of methyl-polysiloxane (MQ), phenyl-methyl- Alkane (PMQ), ethane-acetic acid ethyenyl ester (EVA), high density polyethylene (HDPE) (HDPE), low density polyethylene (LDPE) (LDPE), chlorination it is poly- (ethylene) (CPE), poly- (ethylene, propylene) (EPM), fluoroelastomer (FKM, FFKM) (for example,With) and Their combination.
According at least one embodiment, which includes at least one unsaturated elastomer.In the elasticity The unsaturated elastic body that can be used in body composition includes, for example, Ethylene-Propylene-Diene trimer (EPDM), vinyl silicon Rubber (VMQ), fluorosilicone (FVMQ), nitrile rubber (NBR), acrylonitrile-butadiene-styrene (ABS) (ABS), styrene butadiene rubber Glue (SBR), Styrene-Butadiene-Styrene Block Copolymer (SBS), polybutadiene rubber (BR), styrene-isoprene- Styrene block copolymer (SIS), partially hydrogenated acrylonitrile butadiene (HNBR), natural rubber (NR), the poly- isoamyl two of synthesis Alkene rubber (IR), neoprene (CR), polychloroprene, bromobutyl (BIIR), chlorobutyl rubber and their combination.
According at least one embodiment, which includes the copolymer of at least one saturation.It can be used The non-limiting example of saturated polymer includes ethylene and propylene, butylene, amylene, hexane, heptane, octane and vinyl acetate The copolymer of ester, for example, linear low density polyethylene (LLDPE) (LLDPE), low density polyethylene (LDPE) (LDPE), poly- (ethylene vinyl acetate) (EVA), poly- (ethylene, propylene) (EPM), poly- (ethylene octene) (for example,), poly- (ethylene hexene), poly- (ethylene butene) (for example,)、Polymer (for example, poly- (ethylene methacrylate), poly- (ethylene-acrylate), with And the combination with acrylic acid), with and combinations thereof.
Another embodiment of the invention is related to a kind of object for manufacturing comprising elastic composition as described herein The method of product, wherein this method includes solidifying the elastic composition.
As used in this, term " solidification " refers to the crosslinking of polymer to form reinforcing or hardening polymerization Object.Curing schedule can carry out in any conventional manner.
This method may include a kind of elastic composition as the described herein is extruded to form it is uncured it is pre- at Type article, and make the uncured preforming article solidification.
At least one embodiment of the present invention is related to a kind of method for cured elastomer composition, wherein the composition It forms comprising following item, substantially by following item or is made of following item:
At least one elastomer,
At least one organic peroxide,
At least one compound (for example, 4- hydroxyl-TEMPO (4-OHT)) containing NO free radical, and
At least one compound (for example, mono- tert-butyl hydroquinone (MTBHQ)) containing quinone.This method can further comprise point It opens ground or mixes these components together and in any order to provide the elastic composition.
In at least one embodiment, before the curing schedule, later and/or period, one or more conventional adds Add agent, such as antioxidant (for example, hindered phenol and quinoline of polymerization), aliphatic process oil, processing aid, face Material, dyestuff, tackifier, wax, reinforcing aids, UV stabilizer, foaming agent, coking protective agent, activator, antiozonant or living Property auxiliary agent also may be added in any elastic composition described herein.
The non-limiting example of the application of peroxide preparation of the invention includes using liquid and filler increment etc. HDPE roational molding of the organic peroxide of grade for crosslinking；The production of PEX- pipe；Injection-molded, compression molded, transmitting molding Crosslinking article；Electric wire and cable；Elastomer, rubber and the polymer being usually crosslinked；Modified polymer molecule amount and grafting Reagent such as maleic anhydride (MAH) and glycidyl methacrylate；For producing TPV, (thermoplasticity solidifies rubber to dynamical cure Glue)；And the rubber or foam of polymers of crosslinking.
Embodiment described herein is intended as example of the invention rather than limitation ot it.The ordinary skill of this field Personnel will be appreciated that can be made in the case where not departing from the range of present disclosure for present disclosure these embodiments and The modification of example.The foregoing describe the embodiment of the present invention for using term " including (comprising) " and its variant.So And ladies and gentlemen inventor's it is intended that without departing from the scope of the invention, any of embodiment described herein In person term " including (comprising) " can by " by ... form (consisting of) " and " substantially by ... group At (consisting essentially of) " it replaces.
The present invention further comprises following embodiment
1. a kind of organic peroxide preparation, includes
At least one organic peroxide,
At least one compound containing NO free radical, and
At least one compound containing quinone.
2. organic peroxide preparation as described in claim 1, wherein at least one change containing NO free radical Closing object includes 4-OHT.
3. organic peroxide preparation as described in any of claims 1, wherein the nitrogenous oxygen of at least one from It is at least one or more of of following item by the compound of base: 4- hydroxyl TEMPO (4-OHT) and TEMPO (2,2,6,6- tetramethyl Phenylpiperidines 1- oxygroup).
4. organic peroxide preparation as claimed any one in claims 1 to 3, wherein this is at least one containing quinone Compound includes MTBHQ.
5. organic peroxide preparation according to any one of claims 1 to 4, wherein this is at least containing the chemical combination of quinone Object includes HQMME.
6. organic peroxide preparation as claimed any one in claims 1 to 3, wherein this is at least one containing quinone Compound is at least one or more of of following item: mono- tert-butyl hydroquinone (MTBHQ)；Quinhydrones；The mono- methyl ether of quinhydrones (HQMME)； Mono- amyl hydroquinone and two-amyl hydroquinones.
7. further including at least one such as organic peroxide preparation described in any one of claims 1 to 6 and containing There are the cross linking co-agents of the part at least two functional groups, wherein the functional group is to be selected from the group, the group is by following Composition: it allylic, methaciy lie, acrylic type and can be identical or different.
8. the organic peroxide preparation as described in any one of claims 1 to 7, wherein at least one peroxidating Object includes one in the peroxide of dialkyl group, ketal peroxide, peroxyester, single peroxycarbonates or hydrogen peroxide type Kind is a variety of.
9. a kind of method for manufacturing organic peroxide preparation as described in claim 1, this method includes making At least one organic peroxide, this is at least one containing the compound of NO free radical and at least one change containing quinone Close object mixing.
10. elastic composition as claimed in any one of claims 1-9 wherein, which includes:
At least one elastomer,
At least one organic peroxide,
At least one compound containing NO free radical, and
At least one compound containing quinone.
11. a kind of for solidifying the method for the elastic composition as described in any one of claims 1 to 10, the side Method includes:
Solidify a kind of elastic composition in the presence of oxygen,
Wherein the elastic composition contains comprising at least one elastomer, at least one organic peroxide, at least one The compound of NO free radical and at least one compound containing quinone.
12. a kind of elastomer articles of method according to claim 11 manufacture.
13. a kind of organic peroxide preparation, includes
At least one organic peroxide,
At least one compound containing NO free radical, and
At least one compound containing quinone.
At least one cross linking co-agents
14. organic peroxide preparation as claimed in claim 13, the wherein at least one cross linking co-agents packet Containing the part at least two functional groups, wherein the functional group is to be selected from the group, which is made of following item: allylic, It methaciy lie, acrylic type and can be identical or different.
15. organic peroxide preparation as claimed in claim 13, the wherein at least one cross linking co-agents packet One of coagent described in diphenyl containing 2,4- -4-methyl-1-pentene and optionally claim 14.
16. the organic peroxide preparation as described in any one of claim 13 to 15, the wherein at least one mistake Oxide is selected from the group below a variety of or a variety of peroxide, which is made of following item: dialkyl group, ketal peroxide, peroxide Change the peroxide of ester, single peroxycarbonates or hydrogen peroxide type.
In the present specification, the mode for having enabled to write clear and concise specification to embodiment carries out Description, but intended and will be appreciated that embodiment can differently combine or separate without departing from the present invention.For example, It will be appreciated that all preferred features described herein are suitable for all aspects of the invention described herein.
Following Examples further illustrate that ladies and gentlemen inventor considered for implementing the optimal mode of its invention, and answer This is interpreted the description of the invention rather than limitation ot it.
Example
It abridges used in example.
MH (dN-m)=by point-peak torque that obtains of Newton meter (n.m.) (deci-Newton-meter) meter and the crosslinking that reaches It is related.
The minimal torque of ML (dN-m)=in terms of dN-m.
Ts0.4 (min)=realization increases the time in minutes of 0.4dN-m from minimal torque.
Ts1.0 (min)=realization increases the time in minutes of 1.0dN-m from minimal torque.
Ts2.0 (min)=realization increases the time in minutes of 2.0dN-m from minimal torque.
The time in minutes of total curing time of Tc90 (min)=reach 90%.
Between F=/p- two (t-butylperoxy) diisopropylbenzene (DIPB) (fusible solid peroxide).
IP-D16=t-butylperoxy-isopropenyl cumyl peroxide (liquid peroxide).
D-16=tert-butyl cumyl peroxide (liquid peroxide).
TBEC=OO- t-butylperoxy-O- (2- ethylhexyl) list peroxycarbonates.
4-OHT=4- hydroxyl TEMPO, also referred to as 4- hydroxyl -2,2,6,6- tetramethyl piperidine -1- oxygroups.
HDPE=high density polyethylene (HDPE)
The mono- methyl ether of HQMME=quinhydrones；Also referred to as 4- metoxyphenol (MEHQ)
Mono- tert-butyl-the quinhydrones of MTBHQ=, CAS 1948-33-0.
TAC=triallylcyanurate (cross linking co-agents).
EVA=poly- (ethylene vinyl acetate).
Example 1
Make polyethylene polymer, HDPE (high density polyethylene (HDPE)) is crosslinked in this case, when using 4-OHT and Longer time of scorch is obtained when the synergistic combination of MTBHQ.This blend is matched as being shown as OP-B in table 1 in peroxide Less total additive is used in product, provides significant longer time of scorch value simultaneously for solidification and compounding temperature.
Efficiency=[(MH-ML) × Ts] ÷ (Tc90-Ts),
Wherein about multiple additives to the amount of the crosslinking obtained for peroxide preparation and the curing time of realization Influence, the time of scorch of higher efficiency value instruction greater efficiency.
The synergistic effect of 4-OHT and MTBHQ so that application and method for filler generally can not be resistant to there may be Uniform liquid and fusible solid superoxide composition.
It (includes 4.0% with OP-B that peroxide blends 8.0%4-OHT of the invention, which will be used alone, in OP-A in table 1 The blend of 4-OHT and 2.6%MTBHQ) it is compared.The blend of this additive requires nothing more than 6.6% couple 8.0% of 4- OHT is in OP-A, while at 190 DEG C and there are also produce phase when being crosslinked HDPE polymer at 162 DEG C of mixed temperature When desirable longer time of scorch protection (Ts0.4 and Ts1.0).
Table 1 also shows organic peroxide preparation OP-C, OP-D, OP-E and OP-F, these use two kinds of differences Peroxide IP-D16 andThe 50:50 blend of F.WithF is higher half-life period compared to IP-D16 Peroxide, therefore its decomposition rate is slower at a given temperature and will improve time of scorch and increase curing time.
Additive for amounting to 6.6% in preparation OP-F combined with 4%4-OHT using 2.6%MTBHQ and with Equal or more high load amount be used alone additive compared to provide at 190 DEG C and 162 DEG C it is significant it is longer (Ts0.4 with Ts1.0 time of scorch), as in table 1 for shown in OP-C, OP-D and OP-E.
Example 2
As shown in table 2, by the blend of 4-OHT and MTBHQ and exclusive use 4-OHT together with cross linking co-agents TAC (three Allyl cyanurate) it is compared.Blend according to the present invention, OP-H are provided when being crosslinked HDPE about increased The calculating of the higher efficiency of time of scorch.The total weight of Synergistic blends uses only 6.7% pair 8% for single additive.
Example 3
As shown in table 3, the component of organic peroxide preparation be with equal weight basis at 170 DEG C using having Machine peroxideD-16 (liquid organic peroxide, chemical name are tert-butyl cumyl peroxides) crosslinked EVA It is compared.Blend according to the present invention, OP-J in table 3 provide best group based on MH-ML (dN-m) crosslinking It closes, in addition longest Ts1 and Ts2 (min) time of scorch.The Tc90 time also increases, but based on efficiency calculation time of scorch Increase and good cross-linking properties is greater than the increased compensation to curing time.Synergistic blends are obtained for Ts1 and The good efficiency of both Ts2 values is more than by using equal weight 4-OHT and MTBHQ to be obtained in OP I and OP-K respectively Performance.OP-K provides highest time of scorch value, but MH-ML (dN-m) value seriously reduces, and this significantly reduces incipient scorch Efficiency value, as shown in Table 3.The time of scorch efficiency value of higher calculating is preferred.
Example 4
It is confirmed in example 4 in test #3 using the synergistic benefits of the blend of HQMME and 4-OHT；Table 4 is for making With single peroxycarbonates (for example, OO- t-butylperoxy-O- (2- ethylhexyl) list peroxycarbonates) crosslinked EVA.It crosses Oxide is single peroxycarbonates.OO- t-butylperoxy-O- (2- ethylhexyl) list peroxycarbonates trade name beTBEC。
Compared with the test #1 and #2 that use HQMME or 4-OHT but be not applied in combination, the combination of HQMME and 4-OHT It provides good crosslinking, increased Ts1 and Ts2 time of scorch and provides unexpectedly shorter curing time (base In Tc90min).
When withTBEC allows to mention when being blended using the unexpected synergistic effect of 4-OHT and MTBHQ It (is based on for unexpected good crosslinking with longer Ts1 and Ts2 time of scorch and substantially shorter curing time Tc90 total output therefore) is improved, as confirming efficiency equation.In all peroxide preparations in example 4 Also use TAC (triallylcyanurate) cross linking co-agents.
" efficiency equation "
Efficiency=[(MH-ML) × Ts] ÷ (Tc90-Ts)
Higher efficiency value can indicate to consider time of scorch and the curing time of the greater efficiency including crosslinking.The equation Help the benefit of more final peroxide preparation.Longer time of scorch is desired, but is not with substantially longer Curing time be cost.If people can essentially decreased curing time, while keep or increase time of scorch, then this be Preferably.As determined proof by what is obtained from " efficiency equation ", the novel blend of HQMME and 4-OHT, which provide, to be changed Into whole cross-linking efficiency.

Claims (28)

1. a kind of liquid or fusible solid organic peroxide preparation for solidifying solid elastomers composition, the preparation Product include
At least one organic peroxide between 92wt% and 98wt%,
At least one compound containing NO free radical between 1wt% and 7wt%, this is at least one containing NO free radical Compound includes at least one or more of of following item: 4- hydroxyl TEMPO (4-OHT) and TEMPO (2,2,6,6- tetramethyl piperazine Pyridine 1- oxygroup), and
At least one compound containing quinone between 1wt% and 7wt%, at least one compound containing quinone include following item It is at least one or more of: mono- tert-butyl hydroquinone (MTBHQ)；Quinhydrones；The mono- methyl ether of quinhydrones (HQMME)；Mono- amyl hydroquinone with And two-amyl hydroquinones,
Wherein the organic peroxide preparation can solidify the solid elastomers.
2. organic peroxide preparation as described in claim 1, wherein at least one compound containing NO free radical It is 4- hydroxyl TEMPO (4-OHT).
3. organic peroxide preparation as described in claim 1, wherein at least one compound containing NO free radical It is TEMPO (2,2,6,6- tetramethyl piperidine 1- oxygroup).
4. organic peroxide preparation as described in claim 1, wherein at least one compound containing quinone includes MTBHQ。
5. organic peroxide preparation as described in claim 1, wherein this at least the compound containing quinone includes HQMME.
6. organic peroxide preparation as described in claim 1 further includes at least one containing at least two The cross linking co-agents of the part of functional group, wherein the functional group is to be selected from the group, which is made of following item: allylic, It methaciy lie, acrylic type and can be identical or different.
7. organic peroxide preparation as described in claim 1, wherein at least one peroxide includes dialkyl group, mistake Aoxidize ketal, peroxyester, single peroxycarbonates or hydrogen peroxide type one of peroxide or a variety of.
8. a kind of method for manufacturing organic peroxide preparation as described in claim 1, this method includes making this extremely A kind of few organic peroxide, this is at least one containing the compound of NO free radical and at least one compound containing quinone Mixing.
9. a kind of elastic composition, includes:
At least one solid elastomers and liquid described in claim 1 or fusible solid organic peroxide preparation.
10. a kind of method for cured elastomer composition in the presence of oxygen, which comprises
Cured elastomer composition in the presence of oxygen,
Wherein the elastic composition includes at least one elastomer and liquid described in claim 1 or fusible SOLID ORGANIC mistake Oxide preparation.
11. a kind of elastomer articles of method according to claim 11 manufacture.
12. a kind of liquid or fusible solid organic peroxide preparation for solidifying solid elastomers composition, includes
At least one organic peroxide,
At least one compound containing NO free radical, the compound for containing NO free radical include 4- hydroxyl TEMPO (4- OHT),
At least one compound containing quinone, the compound for containing quinone include that mono- tert-butyl hydroquinone (MTBHQ), quinhydrones, quinhydrones are mono- Methyl ether (HQMME) and mono- amyl hydroquinone and two-amyl hydroquinones,
At least one cross linking co-agents, at least one cross linking co-agents include the part at least two functional groups, Wherein the functional group is to be selected from the group, which is made of following item: allylic, methaciy lie, acrylic type, and can Be it is identical or different,
Wherein the organic peroxide preparation can solidify the solid elastomers.
13. liquid as claimed in claim 12 or fusible solid organic peroxide preparation, the wherein at least one peroxide Compound is one or more peroxide selected from the group below, which is made of following item: dialkyl group, ketal peroxide, peroxidating The peroxide of ester, single peroxycarbonates or hydrogen peroxide type.
14. liquid as described in claim 1 or fusible solid organic peroxide preparation, wherein NO free radical and quinone Combined total amount is between 2wt% and 8wt%.
15. liquid as described in claim 1 or fusible solid organic peroxide preparation, wherein the liquid or can blow Body organic peroxide preparation is can be spraying.
16. liquid as described in claim 1 or fusible solid organic peroxide preparation, wherein the nitrogenous oxygen radical Compound be 4- hydroxyl TEMPO (4-OHT), and the compound containing quinone is mono- tert-butyl hydroquinone (MTBHQ) and/or hydrogen The mono- methyl ether of quinone (HQMME).
17. liquid as claimed in claim 12 or fusible solid organic peroxide preparation, wherein the liquid or fusible Solid organic peroxide preparation is can be spraying.
18. a kind of liquid or fusible solid organic peroxide preparation for solidifying solid elastomers composition, described to match Product includes:
At least one organic peroxide,
At least one compound containing NO free radical, the compound for containing NO free radical are at least one or more of following item Kind: 4- hydroxyl TEMPO (4-OHT) and TEMPO (2,2,6,6- tetramethyl piperidine 1- oxygroup), and
At least one compound containing quinone, which is at least one or more of of following item: mono- tert-butyl hydroquinone (MTBHQ), the mono- methyl ether of quinhydrones, quinhydrones (HQMME) and mono- amyl hydroquinone and two-amyl hydroquinones,
Wherein the organic peroxide preparation can solidify the solid elastomers.
19. organic peroxide preparation as claimed in claim 18, wherein at least one chemical combination containing NO free radical Object includes 4-OHT.
20. organic peroxide preparation as claimed in claim 18, wherein at least one chemical combination containing NO free radical Object is TEMPO (2,2,6,6- tetramethyl piperidine 1- oxygroup).
21. organic peroxide preparation as claimed in claim 18, wherein at least one compound containing quinone includes MTBHQ。
22. organic peroxide preparation as claimed in claim 18, wherein at least one compound containing quinone includes HQMME。
23. organic peroxide preparation as claimed in claim 18, also comprising at least one cross linking co-agents, this is at least A kind of cross linking co-agents include the part at least two functional groups, wherein the functional group is to be selected from the group, the group by Following item composition: allylic, methaciy lie, acrylic type, and can be identical or different.
24. organic peroxide preparation as claimed in claim 18, wherein at least one peroxide include dialkyl group, Ketal peroxide, peroxyester, single peroxycarbonates or hydrogen peroxide type one of peroxide or a variety of.
25. organic peroxide preparation as claimed in claim 18, wherein the liquid or fusible SOLID ORGANIC peroxidating Object preparation is can be spraying.
26. organic peroxide preparation as claimed in claim 25, is sprayed on inert filler.
27. a kind of elastic composition, includes:
Liquid described at least one solid elastomers and claim 18 or fusible solid organic peroxide preparation.
28. a kind of liquid or fusible solid organic peroxide preparation for solidifying solid elastomers composition, described to match Product includes:
At least one organic peroxide,
At least one compound containing NO free radical, the compound for containing NO free radical are 4- hydroxyl TEMPO (4-OHT),
At least one compound containing quinone, which is at least one or more of of following item: mono- tert-butyl hydroquinone (MTBHQ), the mono- methyl ether of quinhydrones, quinhydrones (HQMME) and mono- amyl hydroquinone and two-amyl hydroquinones, and
At least one cross linking co-agents, at least one cross linking co-agents include the part at least two functional groups, Wherein the functional group is to be selected from the group, which is made of following item: allylic, methaciy lie, acrylic type, and can To be identical or different.
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